US6406676B1 - Method of purifying acid leaching solution by precipitation and oxidation - Google Patents

Method of purifying acid leaching solution by precipitation and oxidation Download PDF

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US6406676B1
US6406676B1 US09/551,576 US55157600A US6406676B1 US 6406676 B1 US6406676 B1 US 6406676B1 US 55157600 A US55157600 A US 55157600A US 6406676 B1 US6406676 B1 US 6406676B1
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solution
stage
precipitation stage
precipitation
precipitate
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Jan-Eric Sundkvist
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Boliden Mineral AB
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Boliden Mineral AB
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • C22B23/04Obtaining nickel or cobalt by wet processes
    • C22B23/0453Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • C22B15/0063Hydrometallurgy
    • C22B15/0084Treating solutions
    • C22B15/0089Treating solutions by chemical methods
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00Obtaining zinc or zinc oxide
    • C22B19/20Obtaining zinc otherwise than by distilling
    • C22B19/26Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Definitions

  • the present invention relates to a method of purifying an acid leaching solution which has been obtained by hydrometallurgically working-up material that contains valuable metals, and that in addition to said valuable metals also includes Fe 3+ and Fe 2+ and possibly also arsenic in solution.
  • the method can be used generally for acid leaching solutions of this nature regardless of the choice of hydrometallurgical process applied and the type of starting material, it is particularly suitable for purifying acid leaching solutions that result from bioleaching processes, i.e. processes in which bacteria are used to accelerate the leaching process.
  • Bioleaching is described generally in our earlier Patent Publications U.S. Pat. No. 5,397,380 and SE-A-9901613-1, and, for instance, also in WO 9216667 which deals generally with the oxidation of metal sulphide material with thermo-tolerant bacteria and also in WO 94/28184 which relates to bioleaching of zinc concentrate.
  • a relatively large percentage of the iron in a bioleaching solution is present in divalent form, Fe 2+ , and it is necessary to convert all iron to a trivalent form, i.e. Fe 3+ , by oxidation in order to be able to separate the iron from remaining metals (valuable metals) by precipitation.
  • This is normally effected at a pH>3 by injecting air into the system so as to obtain a sufficiently rapid kinetic, in other words a high oxidation rate.
  • some precipitation of other metals will take place, caused by inclusions in the resultant voluminous iron hydroxide precipitate among other things, and consequently valuable metals will be lost in the precipitate to an extent which is economically significant with respect to most valuable metals.
  • the drawing is a flowchart illustrating one embodiment of the invention.
  • the object of the present invention is to greatly reduce the extent of the problems associated with the co-precipitation of valuable metal contents when purifying the aforedescribed acid leaching solutions.
  • the inventive method is characterised to this end by the method steps set forth in the accompanying Claims.
  • the major part of the Fe 3+ -content and arsenic content of the leaching solution is precipitated out in a first stage, by adding pH-elevating agent to the leaching solution.
  • the precipitate formed in the first stage is separated from the solution and removed from the process.
  • the precipitate-free solution is then oxidised in a second precipitation stage while adding additional pH-elevating agent to oxidise Fe 2+ and therewith precipitate out the resultant Fe 3+ and any arsenic that remains in the solution.
  • the precipitate formed and any solid pH-elevating agent that remains is/are extracted from the solution and returned to the process to more acid conditions, and the thus purified, or cleansed, solution is then processed to recover its valuable metal content in a manner known per se.
  • the pH is conveniently raised during the first process stage to a value lying in the range of 2.2-2.8, and is raised in the second process stage to a value lying in the range of 3.0-4.5. Oxidation in the second process stage is conveniently effected by injecting air into the solution.
  • the pH-elevating agent may suitably be lime or limestone, although it will be understood that local conditions and possible access to other inexpensive and useful alkaline materials may be a deciding factor in this respect.
  • All or part of the solid material extracted from the second process stage may conveniently be returned to the first process stage, therewith utilising the added alkaline material to a maximum.
  • Part of the separated solid material obtained in each precipitation stage may be returned within respective stages as a nucleating agent.
  • the only part of the precipitate obtained in the second process stage that is not returned to the first stage is the part which then circulates internally within said stage.
  • a sulphuric acid leaching solution containing iron, arsenic and also valuable metals that shall be won from the solution in later process stages is delivered together with lime to a reactor equipped with agitating or stirring means, or to a series of such reactors, for carrying out the first precipitation stage, which is effected by increasing the pH of the solution to a final value of 2.2-2.8.
  • the major part of the trivalent iron present in the solution is precipitated together with any arsenic present.
  • As much as 90-95% of the trivalent iron content and a significant part of the arsenic can be precipitated without risk of any co-precipitation of other metals.
  • the resultant slurry is de-slimed.
  • a final iron-arsenic-gypsum precipitate free from valuable metal can be removed from the process and further filtered, including a number of washing stages or counterflow washing of the precipitate in a thickener or thickeners, and then transported to a waste dump.
  • the washing liquid is suitably recovered and returned as leaching solution to the bioleaching stage.
  • the overflow from the thickener downstream of the first precipitation stage will be relatively turbid if no flocculating agent has been added, since the overflow is led into the first reactor of a series of reactors in the second precipitation stage, together with lime or limestone.
  • the divalent iron present is oxidised in this second precipitation stage, by injecting air into the solution and raising its pH to a final value of about 3.0-4.5.
  • the precipitate obtained in the second precipitation stage is delivered to a thickener, suitably together with a flocculating agent, downstream of the last reactor in said second stage; the precipitate should really be referred to as a slurry in this stage of the process, because of its voluminous and fluffy physical consistency in a highly liquid environment.
  • the thickened slurry obtained in the second thickener and possibly containing co-precipitates of valuable metals. in hydroxide form is returned and fed into the first reactor in the first precipitation stage together with the acid leaching solution, where the--conditions prevailing in the process are as acid as possible. All co-precipitates and any unreacted lime will be effectively dissolved in the more acid environment.
  • some of the thickened slurry obtained in the second thickener may be recycled to the second precipitation stage with the object of improving crystallisation in the precipitation process in this stage.
  • the method according to the invention affords a number of advantages, some of which include
  • iron/arsenic precipitates can be washed effectively by withdrawing the product from the circuit at low pH, and as a result of the low addition of flocculating agent.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Removal Of Specific Substances (AREA)
US09/551,576 1999-06-01 2000-04-18 Method of purifying acid leaching solution by precipitation and oxidation Expired - Lifetime US6406676B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE9902008 1999-06-01
SE9902008A SE514338C2 (sv) 1999-06-01 1999-06-01 Förfarande för rening av sur laklösning

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US6406676B1 true US6406676B1 (en) 2002-06-18

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US (1) US6406676B1 (ru)
EP (1) EP1059361A1 (ru)
AU (1) AU761108B2 (ru)
CA (1) CA2306015C (ru)
EA (1) EA002674B1 (ru)
MX (1) MXPA00005341A (ru)
PE (1) PE20010341A1 (ru)
SE (1) SE514338C2 (ru)
ZA (1) ZA200002201B (ru)

Cited By (27)

* Cited by examiner, † Cited by third party
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US20060048828A1 (en) * 2004-09-03 2006-03-09 Ranco Incorporated Of Delaware Reversing valve with flowsplitter
US7399454B2 (en) 2004-04-29 2008-07-15 Metalox International, Llc Metallurgical dust reclamation process
US20090145856A1 (en) * 2007-12-11 2009-06-11 Raymond Letize A Acid recycle process with iron removal
US7615199B2 (en) 2005-05-03 2009-11-10 Outotec Oyj Method for the recovery of valuable metals and arsenic from a solution
US20100255559A1 (en) * 2007-10-31 2010-10-07 Molycorp Minerals, Llc Apparatus and process for treating an aqueous solution containing biological contaminants
US20110002971A1 (en) * 2009-07-06 2011-01-06 Molycorp Minerals, Llc Ceria for use as an antimicrobial barrier and disinfectant in a wound dressing
US20110044869A1 (en) * 2007-05-21 2011-02-24 Richard Boudreault Processes for extracting aluminum and iron from aluminous ores
US8066874B2 (en) 2006-12-28 2011-11-29 Molycorp Minerals, Llc Apparatus for treating a flow of an aqueous solution containing arsenic
US8252087B2 (en) 2007-10-31 2012-08-28 Molycorp Minerals, Llc Process and apparatus for treating a gas containing a contaminant
US8349764B2 (en) 2007-10-31 2013-01-08 Molycorp Minerals, Llc Composition for treating a fluid
US8475658B2 (en) 2003-01-29 2013-07-02 Molycorp Minerals, Llc Water purification device for arsenic removal
WO2014177903A1 (es) * 2013-04-29 2014-11-06 Servicios Condumex S.A. De C.V. Procedimiento de biolixiviacion y estracción por disolventes con recuperación selectiva de cobre y zinc a partir de concentrados polimetálicos de sulfuros
US9023301B2 (en) 2012-01-10 2015-05-05 Orbite Aluminae Inc. Processes for treating red mud
US9150428B2 (en) 2011-06-03 2015-10-06 Orbite Aluminae Inc. Methods for separating iron ions from aluminum ions
US9181603B2 (en) 2012-03-29 2015-11-10 Orbite Technologies Inc. Processes for treating fly ashes
US9233863B2 (en) 2011-04-13 2016-01-12 Molycorp Minerals, Llc Rare earth removal of hydrated and hydroxyl species
US9260767B2 (en) 2011-03-18 2016-02-16 Orbite Technologies Inc. Processes for recovering rare earth elements from aluminum-bearing materials
US9290828B2 (en) 2012-07-12 2016-03-22 Orbite Technologies Inc. Processes for preparing titanium oxide and various other products
US9353425B2 (en) 2012-09-26 2016-05-31 Orbite Technologies Inc. Processes for preparing alumina and magnesium chloride by HCl leaching of various materials
US9382600B2 (en) 2011-09-16 2016-07-05 Orbite Technologies Inc. Processes for preparing alumina and various other products
US9410227B2 (en) 2011-05-04 2016-08-09 Orbite Technologies Inc. Processes for recovering rare earth elements from various ores
US9534274B2 (en) 2012-11-14 2017-01-03 Orbite Technologies Inc. Methods for purifying aluminium ions
US9885095B2 (en) 2014-01-31 2018-02-06 Goldcorp Inc. Process for separation of at least one metal sulfide from a mixed sulfide ore or concentrate
CN107915291A (zh) * 2017-11-17 2018-04-17 金川集团股份有限公司 一种利用废水沉砷渣对含砷硫酸铜溶液进行除砷的方法
US9975787B2 (en) 2014-03-07 2018-05-22 Secure Natural Resources Llc Removal of arsenic from aqueous streams with cerium (IV) oxide compositions
CN109574319A (zh) * 2019-01-07 2019-04-05 紫金矿业集团股份有限公司 有色金属冶炼高砷污酸的固砷工艺
CN109607872A (zh) * 2019-01-07 2019-04-12 紫金矿业集团股份有限公司 一种含砷污酸的综合利用及砷的安全处置方法

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US7314604B1 (en) * 1999-09-30 2008-01-01 Billiton Intellectual Property, B.V. Stable ferric arsenate precipitation from acid copper solutions whilst minimising copper losses
US6843976B2 (en) * 2001-02-27 2005-01-18 Noranda Inc. Reduction of zinc oxide from complex sulfide concentrates using chloride processing
US7455715B2 (en) 2001-07-13 2008-11-25 Teck Cominco Metals Ltd. Heap bioleaching process for the extraction of zinc
CA2353002C (en) 2001-07-13 2009-12-01 Teck Cominco Metals Ltd. Heap bioleaching process for the extraction of zinc
WO2009114903A1 (en) * 2008-03-20 2009-09-24 Bhp Billiton Ssm Development Pty Ltd Process for the recovery of nickel and/or cobalt from high ferrous content laterite ores
CN104846199A (zh) * 2015-06-10 2015-08-19 云南驰宏锌锗股份有限公司 一种脱除硫酸铜溶液中铁、砷的方法

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US3510259A (en) 1967-07-13 1970-05-05 Union Carbide Canada Ltd Simultaneous leaching of zinc and manganese ores
JPS4935516A (ru) * 1972-08-11 1974-04-02
US3985856A (en) 1975-02-06 1976-10-12 Continental Oil Company Removal of iron from aqueous acid solutions containing iron and copper
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DE125827C (ru) 1901-04-03 1901-12-07
US3510259A (en) 1967-07-13 1970-05-05 Union Carbide Canada Ltd Simultaneous leaching of zinc and manganese ores
JPS4935516A (ru) * 1972-08-11 1974-04-02
US3985856A (en) 1975-02-06 1976-10-12 Continental Oil Company Removal of iron from aqueous acid solutions containing iron and copper
JPS533992A (en) * 1976-06-30 1978-01-14 Daido Kagaku Sochi Recovery and treating process for waste sulfuric acid
US4241039A (en) 1977-12-14 1980-12-23 Dowa Mining Co. Ltd. Method of removal of arsenic from a sulfuric acid solution
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JPS5840191A (ja) * 1981-09-04 1983-03-09 Dowa Koei Kk 含砒素・硫酸第1鉄溶液の脱砒処理法
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Cited By (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8475658B2 (en) 2003-01-29 2013-07-02 Molycorp Minerals, Llc Water purification device for arsenic removal
US7399454B2 (en) 2004-04-29 2008-07-15 Metalox International, Llc Metallurgical dust reclamation process
US20060048828A1 (en) * 2004-09-03 2006-03-09 Ranco Incorporated Of Delaware Reversing valve with flowsplitter
US7615199B2 (en) 2005-05-03 2009-11-10 Outotec Oyj Method for the recovery of valuable metals and arsenic from a solution
US8066874B2 (en) 2006-12-28 2011-11-29 Molycorp Minerals, Llc Apparatus for treating a flow of an aqueous solution containing arsenic
US20110044869A1 (en) * 2007-05-21 2011-02-24 Richard Boudreault Processes for extracting aluminum and iron from aluminous ores
US8241594B2 (en) 2007-05-21 2012-08-14 Orbite Aluminae Inc. Processes for extracting aluminum and iron from aluminous ores
US8337789B2 (en) 2007-05-21 2012-12-25 Orsite Aluminae Inc. Processes for extracting aluminum from aluminous ores
US8597600B2 (en) 2007-05-21 2013-12-03 Orbite Aluminae Inc. Processes for extracting aluminum from aluminous ores
US20100255559A1 (en) * 2007-10-31 2010-10-07 Molycorp Minerals, Llc Apparatus and process for treating an aqueous solution containing biological contaminants
US8252087B2 (en) 2007-10-31 2012-08-28 Molycorp Minerals, Llc Process and apparatus for treating a gas containing a contaminant
US8349764B2 (en) 2007-10-31 2013-01-08 Molycorp Minerals, Llc Composition for treating a fluid
US8557730B2 (en) 2007-10-31 2013-10-15 Molycorp Minerals, Llc Composition and process for making the composition
WO2009075710A1 (en) * 2007-12-11 2009-06-18 Macdermid, Incorporated Acid recycle process with iron removal
US20090145856A1 (en) * 2007-12-11 2009-06-11 Raymond Letize A Acid recycle process with iron removal
US20110002971A1 (en) * 2009-07-06 2011-01-06 Molycorp Minerals, Llc Ceria for use as an antimicrobial barrier and disinfectant in a wound dressing
US9945009B2 (en) 2011-03-18 2018-04-17 Orbite Technologies Inc. Processes for recovering rare earth elements from aluminum-bearing materials
US9260767B2 (en) 2011-03-18 2016-02-16 Orbite Technologies Inc. Processes for recovering rare earth elements from aluminum-bearing materials
US9233863B2 (en) 2011-04-13 2016-01-12 Molycorp Minerals, Llc Rare earth removal of hydrated and hydroxyl species
US9410227B2 (en) 2011-05-04 2016-08-09 Orbite Technologies Inc. Processes for recovering rare earth elements from various ores
US9150428B2 (en) 2011-06-03 2015-10-06 Orbite Aluminae Inc. Methods for separating iron ions from aluminum ions
US9382600B2 (en) 2011-09-16 2016-07-05 Orbite Technologies Inc. Processes for preparing alumina and various other products
US10174402B2 (en) 2011-09-16 2019-01-08 Orbite Technologies Inc. Processes for preparing alumina and various other products
US9556500B2 (en) 2012-01-10 2017-01-31 Orbite Technologies Inc. Processes for treating red mud
US9023301B2 (en) 2012-01-10 2015-05-05 Orbite Aluminae Inc. Processes for treating red mud
US9181603B2 (en) 2012-03-29 2015-11-10 Orbite Technologies Inc. Processes for treating fly ashes
US9290828B2 (en) 2012-07-12 2016-03-22 Orbite Technologies Inc. Processes for preparing titanium oxide and various other products
US9353425B2 (en) 2012-09-26 2016-05-31 Orbite Technologies Inc. Processes for preparing alumina and magnesium chloride by HCl leaching of various materials
US9534274B2 (en) 2012-11-14 2017-01-03 Orbite Technologies Inc. Methods for purifying aluminium ions
US20160115564A1 (en) * 2013-04-29 2016-04-28 Servicios Condumex S.A. De C.V. Method for bioleaching and solvent extraction with selective recovery of copper and zinc from polymetal concentrates of sulfides
AU2013388340B2 (en) * 2013-04-29 2018-08-23 Servicios Condumex S.A. De C.V. Method for bioleaching and solvent extraction with selective recovery of copper and zinc from polymetal concentrates of sulfides
WO2014177903A1 (es) * 2013-04-29 2014-11-06 Servicios Condumex S.A. De C.V. Procedimiento de biolixiviacion y estracción por disolventes con recuperación selectiva de cobre y zinc a partir de concentrados polimetálicos de sulfuros
US10280481B2 (en) * 2013-04-29 2019-05-07 Servicios Condumex S.A. De C.V. Method for bioleaching and solvent extraction with selective recovery of copper and zinc from polymetal concentrates of sulfides
US9885095B2 (en) 2014-01-31 2018-02-06 Goldcorp Inc. Process for separation of at least one metal sulfide from a mixed sulfide ore or concentrate
US10370739B2 (en) 2014-01-31 2019-08-06 Goldcorp, Inc. Stabilization process for an arsenic solution
US11124857B2 (en) 2014-01-31 2021-09-21 Goldcorp Inc. Process for separation of antimony and arsenic from a leach solution
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CN109574319A (zh) * 2019-01-07 2019-04-05 紫金矿业集团股份有限公司 有色金属冶炼高砷污酸的固砷工艺
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CN109607872B (zh) * 2019-01-07 2021-11-19 紫金矿业集团股份有限公司 一种含砷污酸的综合利用及砷的安全处置方法
CN109574319B (zh) * 2019-01-07 2021-11-19 紫金矿业集团股份有限公司 有色金属冶炼高砷污酸的固砷工艺

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ZA200002201B (en) 2000-11-14
EA200000476A2 (ru) 2000-12-25
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